Esters of hydroxy acetylated blown ricinoleic acid compounds with oxyalkylated phenol aldehyde resins



least;-l4\;-and notimore than 1 2V-ca bona1foms --rsubs,tituted in the2;4;6 ;;p sition; ;said; :5 -;.-;kylated resinbeing;characterizedhm-thcint odu z tion 3 into the i resin imolecule of:a i plurality of Patented Jan. 1 952 UNITED STATES ee o lasts-asormnaQX csrrmrr eicwu ,momorsrc [ACID COMPQUNDS 'WITH oxrAt rtemo" manorMelvin zDe Bronte, :St. Louis FLU F-$ 1P sKeisenw hsterGrov s, Mo.signorstoz iptrozlite, p retiqalit i ag-$ 3! De i. a 90 no ra rpe irajNoDrawing. Appl ication December lfi,1948, Sei-ial No. 6:1;4-47

.fIhe :apresent aimrention is concerned with zeal:- tainlnewchemicalaproducts.,nompounds,' r corn: positions,.-whichhave;-usefulapplicationsii ous :a-rts. This invention is :acontinuatiominpart of our -coepending application, :Serial :No.-734;-202;fi1ed Maren-l2, 19a? andnowabandoned. zIt :includes methodsiorlprocedures for :ma-nufamturing said new chemical products, gcomponnds,'or' :compositions, as well :as the products, room- -pcunds orcompositions themselves.

:Saidnew compositions;are-testers zin which the ccyl *radical -isthatiof thee-fatty acid ;of .a hyadroxyacetylated drastically-oxidizedricinol'eic compound selected from the class "consisting of castor oil,triricinolein, 'diricinolein, :monoricin- =clein, superg'lyceri-nate'dcastor i-oil, :castor 4011 -estoli'des, polyricinoleic acid, andmicinoleic :acid, and the alcoholic radical is-thatof certain hyd-rophile pol-yhydric "synthetic :pro ducts asaid 'drophile =-syntheticproducts ibeing oxyalkylation products of '-'(-'A) an alpha-betaallcylene oxide lraving not more than {4 carbon atoms and selected fromthe class consisting of ethylene oxide, propylene oxide, butyleneoxideiaglycide and methylglycide, and B)--an--oxya-lkylationsolvent-soluble, water-insoluble phenol-aldehyde resin;saidre- ;sintbeing derived by reaction between a difunctionalzmonohydrici phenolzandlnna aldehyde shavzing not vover i 8 carbon atomsrand reactive towardlsaidphenol;rsaidsresinzbeingsiormedzimthesubstantial absence .cf .trifunctionalzphenols; rsaid phenol being of.theiormule.

Wh L .i iarhrdracerbon aiice movin 1%? divalent: radicals ,:hav inglthetorrnula 211.511! Whi ZJRI isle-1 m mber fi-esel t d irolm theiclass consi in eth e egrad ca smrop lena adi- :c l butylene.radicals,:...:hydroxypropyl n rad cals, andhydroxybutylene;radica1$.:;andn; --is;-; a numeralvvaryin s Qm";1t-:;:t20; w th'atherprc iso ;.that: at least 1-2 moles;v of salkyleneroxidh s i troduced for@eachephenolicghucleus.

Althou h; the herein; describedproducts ghaye a number ofindustrialiapplicationsathey .areiof :particular walue for;-resolvingipetroleiun emulsionsof the waterg-ineoik typezthat'areicommonly :srcferred-z to as fcntaoilf' "fro'ily: 5011;? "emulsi-fied1 oil," etc., and which comprise fine droplets ofnaturallymccurringwaters :or brines dispersed ina more orlesspermanentstate throughout the oil whichconstitutes thecontinuous phaseof the emulsion. This specific application is'describedand claimed inour co-pendingtapplicagtien, -Seria1 No.-'64,446, filed December 10,1948, now -l=fatent 2,54l,99 2, issued February 20, (1951. -See--alsoour co-pending application, Serial No. {54,469, ii-led December 10,1948. The new productsareuseful as wetting, detergent and levellingagents in the laundry, textile and dyeing industries; as wetting agentsand detergents in the acidwashing of building stone :and brick; .aswetting; agents and spreaders in the application of asphalt-inroadbuilding'and the like; as a notation reagent in the flotationseparation of various aqueous suspensions containing negativelyi chargedparticles such as vsewage, coal washing a waste water, and various tradewastes 2o and-the like; as germicides,=insecticides, emulsiixingagents,as-for example, for cosmetics, spray oils, water-repellenttextile finishes; as lubrieants, etc.

The -oxyalkylated resins, used to provide the 25231100110110radical-ofthe new. esters, are described in our Patents 2 499570,granted March -7,- 1950, and-'=2;54l;991,grantedFebruary '20, 1951, and-refe eince is inade to those-patents fona descrip- -tio n of-the'-phenolaldehyde resins used and their oxyalkylat'iontoproduce thealcoholic products. For specific examples of theresins-reference is :madto-;Examp1'es 1a through 103a of Patent 2,4993%. For ex-amplesof-theoxyalkylated products, reference is made to Examples -1bthrou'gh 18b ofPatent -ZAQQB'ZO-and to the tables which T 'appear in columns 51*through V 56 thereof, and also made ---to the tables which appear atcolumns 31 through 46 of =Patent-2,54l,9 9l. The hydifoxy acety-lateddrastically-oxidized ricinoleic Qi mpolmds whichprovide-the acylradicals of the new esters are described in detail in Patent 2375;530,grant'ed lvlay 8, i945, and -reference is; made to that patent fordescription of these products} -For-speci fice amp1es of theseproducts-rj ference is made 'to- Examples 1"through -4 iihi ra I iltwill be noted that having obtained a compound which is essentially a-polyhydric alcohol, ".i.- e., an oxya'llryl ate'dresin cfthe" typeherein 'coriteinpiated, 'ne can produce esters by any one of the, yariois procedures employed for produc n s ers; o idetereent-icrmina id f h'l com n polrhydrkifimhds .i A i wel -K11 72511 ne may emb o no onl hfatt ac i se 51; rsa tab i aeiea rh rama i istance, the acylchloride,the anhydride etc. in

some instances, trans-esterification or cross- .radical is replaced byan ester radical.

esterification will be employed. For instance, the oxyalkylatedderivatives can be heated with the methyl or ethyl ester of the selectedacid or selected hydroxy-acetylated drastically-oxidized compound, inpresence of the alkaline catalyst, so

as to eliminate methyl or ethyl alcohols. Trans- Y esterification orcross-esterification can be em- An acidic hydroxyacetylateddrastically-oxidized ricinoleic acid compound having a free ricinoleicacid earboxyl is obtained in the manner previously described, or someobvious modification thereof. ricinoleic acid, or triricinoleic acid, ora mixture thereof, is subjected to drastic oxidation and then tohydroxyacetylation. The product is analyzed to determine its acid value.An alter- For instance, ricinoleic acid, di-

nate procedure is to employ a hydroxyacetylated drastically-oxidizedricinoleic acid compound and to subject it to acid saponification so asto yield the corresponding fatty acids. In any event, an oxyalkylatedderivative, such as Example 12212 of Patent 2,541,991, is esterifiedwith a hydroxyacetylated drastically-oxidized ricinoleic acid compoundin acidic form, in an amount sufiicient to convert approximatelyone-fourth of the polyglycol radicals into the fatty acid ester. Thehydroxyl value of the oxyalkylated derivative can be calculated withoutdetermination, I

based on the hydroxyl value and weight of the phenol-aldehyde resinoriginally employed, plus the increase in weight after oxyalkylation. Ifglycide or methylglycide is employed, allowance must be made for thepolyhydric character of the oxyalkylating reactant. In any event, ifdesired, the hydroxyl value of the oxyalkylated product can bedetermined by the Verley-Biilsing method, or any other acceptableprocedure. The

esterification reaction is conducted in any con ventional manner, suchas that employed for the preparation of the higher fatty acid esters ofphenoxyethanol.

Fatty acids of the kind described, 1. e., hydroxylateddrastically-oxidized fatty acids, show at' least some solubility in theoxyalkylated derivatives of the kind shown in the previous examples,even though this is not necessarily true of the glycerides of the fattyacids. stance reference is made to the oxyalkylated derivatives inabsence of a solvent. Since esterification is best conducted in asystem, it is our preference to add xylene, or even a higher boilingsolvent such as mesitylene, cymene, tetralin or the like and conductesterification in such consolute mixture. It is not necessary to add allthe fatty acid at one time. One may add a quarter or half the totalamount to be esterified, and after such portion ofthe reactant hascombined, then add more of the specifically described fatty acid. Thesolubility of the specifically described fatty acid, of course,increases as the hydroxyl This is also true if one resorts totrans-esterification or cross-esterification with the glyceride or lowmolal alcohol ester.

In this inv water was equal to at least theoretical.

Our preference is to have present a substantial amount of xylene orhigher boiling, waterinsolublesolvent, and to distill under a refluxcondenser arrangement, so that water resulting from esterification isvolatilized and condensed along with the xylene vapor in a suitablyarranged trap. The amount of xylene employed is approximately equal toone-half the weight of the mixed reactants. The water should be removedfrom the trap, either manually or automatically, and the xylene returnedcontinuously for further distillation. Such reaction is hastened if asmall amount of dry hydrochloric acid gas is continuously injected intothe esterification mixture. When the reaction is completed, the xyleneis removed by distillation. Small amounts of unreacted, specificallydescribed fatty acid can be converted into the methyl or ethyl ester andremoved by vacuum distillation, or permitted to remain. For example, anexcess .of anhydrous ethyl alcohol may be added, and .reacted so as toesterify any residual specifically described fatty acid, and then suchexcess of ethyl alcohol may be distilled off as a alcohol-5% watermixture, and thus, the water resulting from esterification with thealcohol can be removed.

However, even where the amount of specifically described fatty acidemployed is stoichiometrically equal to the hydroxyl radicals present,we have not found it desirable to take any undue precautions toeliminate any residual specifically described fatty acid. As a matter offact, numerous'examples include the present one and those subsequentlydescribed which yield partial or fractional esters in which there areresent residual hydroxyl radicals. Under such circumstances there aresubstantially no free fatty acid radicals present, and the productsobtained by partial esterification, instead of complete esterification,represent the most valuable type. A sulfonic acid, such as toluenesulfonic acid, may be added in amounts of to 1% to act as a catalyst.

As a specific example the following ratios were -used:

Grams Xylene-containing oxyalkylated resin 12212 of Patent 2,541,9911110 Product identified as Example 1 of Patent 2,375,530 263 Xylene 250Para-toluene sulfonic acid 15 The above mixture was placed in a refluxvessel with appropriate condenser and refluxed at a temperature of to(2. for approximately 4 to 6 hours, but in any event until the amount of(4.5 cc.) Our experience has been, however, that due to moisture in thecomponents or due to etherization, or for some other reason, the yieldof water is apt to be 10% to 15% higher by the time the reaction hasgone to completion or equilibrium.

The oxyalkylated resins vary from tacky solids to thick, viscousliquids, and the color varies 'from'a light amber-almost water-white-toa dark or blackish color, particularly a reddishshort of the sub-rubberystage. The esters oh- 4 tained are apt to show physical properties, asfar as viscosity and color go; somewhat. intermediate betweenthe samepropertiesj oi the i itialreactants'. Attimc s, they may be evenmoreviscous and: We n es Example 2d The same procedure was followed asin Example.- lci, preceding; except that the amountof describedhydroxyacetylated drastically-oxidized ricinoleic acid compound. fattyacid employed was suflicient to convert one-half; of the'polyglycolradicals into esterfo'rm.

The following ratios. were used in a. specific e ample: i

Grams Xylene-containing oxyalkylatedresin 118bof Patent 2,54l,991 1294Product identified" as Example 3- of Patent -2-,375,530 600 Xylene 200Para-toluene sulfonic-acid. I2

procedureemployed was the same. as in Example 1d,; preceding except.that. the amoi nt of water evolved was approximately cc.

m l fid.

The. same procedure was. followed as in Ex.- ample. 1d, preceding,except that theamounti-oi' described hydroxyacetylateddrastically-oxidized and h re i c sl adv 'ricinoleic acid: compoundfatty acid; employed.

was sufficientto. convert. three-fourthsrof: the polyglycolradicals-into: ester form.

Thefollowing: ratios were 1 1 S, &di in. a specific example:

. Grams. xrl neecontamine oxyalkylsted resin. 19512- 0:-

Pat nt 2,541,9 1 :1

m uct identified; s xamie 3 f ace The procedure employed" was-the;vsame; as; in Example 1d, preceding. The amount of water evolvedwaszapproximatelylizcc.

E amels-4d The same procedure wasf'ollowedas in- Example 1d; preceding,except that the amount of described hydroxyacetylat'eddrastically-oiiidizedf Gra ns eme rqeclsrei ss followeds amp e-1.d-prece lins. exceptthat the amount of water evolved was approximately18. 5 cc.

2,375,530 525 Xylene- .-r. .150 Par oluene su f...i ac id 8 Theprocedure employed was the same as am le d, pr din an hie-reac on was spnped when?) cc. of water had'been eliminated.

Example 611 The same procedure was followed as in Examples ld'to4d,.preceding; except that the-oxyalkylatecl resin employed was the oneexemplified by Example "d of" Patent 2,541,991. The following ratioswere employed in a specific example:

r Grams Xylene-ccntaining oxyalkylated resin 1251) of Patent. 2,541,il9l511 Product identified as Example=3 of Patent $375,530 1200 Xylene? 250Para-toluene sulfonic acid 14 The procedure followed was the. same as.in,Ex.- ample Id, preceding, except that. atv the end of the reactionperiod (6. hours); they amount of water evolved was 1815 grams,

Example 7d The same procedure was followed. as; in the precedingexamples', except that the, reaction was conducted by means of the ethylor methylicster instead of; a correspondingacid- The ethyl or methyl;ester can ice-obtained in any; one of various ways. The m.ev, i Q11sdescription includes. the hydroxyacetylation of; the ethyl or methylester of ricinoleic acid; diricinoleic' acid' or; triricinoleic acid,preceded by drasticioxidation, Aprocedure equally suitable. is toobtainav similar derivative from theglyceridei. towit, a product of thekind described under the headings; of Examples 1- to 4 of; Patent;2,375,530,,inclusive. Suchproduct can be converted into theimethylorethyl. ester Icy-the usual alcoholysis; proceeding, employing anhydrousmethyl alcohol, or'anhydrous ethyl alcoholand a catal'yst, suchas an;alkaline material. Such. procedure; is conventional; see, for example-Urs Patent No. Rea-2,751, reissued April 30, .1946, to Trent. In suchprocedure the liberated glycerol, is-disca-rded, Wepreier to. use the,methyl; or ethyl; ester obtained by the transposition of ahydrozgyacetylated drasticallyoxidized triricinolein; Thevreactioninvolvi ng the seCond transposition with the oxyalkylatedthermopla stic resin is preferably-conducted in the absenceoi anysolvent, or; if a, solvent be em.-- ployed;; it should be 'fairlyi highboiling, such; as xylene, Instead of using; anacid catalyst. an alkalisuch; as; caustic soda, or: sodium. methylate s em ere The amounfirsed.variesrrcmgonee tend ng l%..,t,c,.-. 11%. areraeevalue may: he.

in the neighborhood of one-half of 1%. The

reaction is conducted preferably with the methyl ester, which resultsin" the elimination of methait is to be noted that by varying theamounts of the methyl ester added to the oxyalkylated resin one canintroduce varying proportions of the acyl radical just as readily as ifthe acid itself were employed. It is intended, of course, to contemplatean entire range of such compounds comparable to those previouslydescribed. Obviously, completeness of reaction can be determined in anyone of a number of ways, such as determination of the amount of lowmolal alcohol volatilized.

Example 8d The same procedure was followed as in the preceding examples,except that the esters were produced by cross-esterification ortrans-esterification, employing the glyceride so as to result in theformation of a non-volatile alcohol instead of a volatile alcohol as inthe preceding examples. The catalyst employed was an alkaline catalystand the temperature employed was approximately.

200 C. to 225 C. The time of reaction may vary somewhat, but generallyrequires 3 to 8' hours. The temperature should be high enough to insuretrans-esterification in presence or the alkaline catalyst but in anyevent should be below the point of pyrolysis as far as the oxyalkylatedderivative of the fatty acid compound is concerned. As a rule, pyrolysismay take place at anytemperature above 250 C. We prefer to conduct thereaction by simply employing derivatives of the kind described under theheadings of Examples 1 to 4 of Patent 2,375,530, inclusive, and mix suchreactants with the appropriate amount of oxyalkylated resins of the kinddescribed so that if reaction is complete and all the acyl groupsoriginally attached tothe glycerol radical become transposed to thepolyglycerol radical, then by using variations of reactants one willobtain the same range, as described under the previous headings ofExamples id to 6d, preceding. I

In reactions of this kind with the liberation of a non-volatile alcoholit is quite likely that the reaction does not go to completion. However,the

equilibrium apparently permits a significant'or substantial yield, duein part to the fact that the glycerol forms polyglycerols withcomparative ease, whereas, the hydroxyl radicals of the oxyalkylatedderivatives my etherize to a lesser degree. There is also thepossibility that, in part, the glycerol may etherize with. theoxyalkylated derivative. This brings about the same result as if theoxyalkylated derivative had been treated with a mole of glycide as aterminal reactant.

The solubility of the esters shows variation of substantially the samekind shown by the oxyethylated resins except, as a rule, anyesterification tends to decrease solubility in water (subject to theexceptional instances noted in the preceding paragraph) and perhaps to alesser extent in polar solvents tends to increase solubility in organicsolvents particularly in non-polar organic solvents. This is obviousinsofar that the esters herein contemplated need not be total esters butmay be fractional as well. Thus, the range of esters includes such widevariations incomposh tion and solubilities.

As has been pointed out previously the esters as prepared in previousexamples usually have a solvent, such as xylene or the like, present.Our preference is to leave such solvent present when the products areemployed for demulsii'lcation or similar purposes. Needless to say, thesolvent can be eliminated by evaporation or distillation, includingvacuum distillation. If desired, the final product can be neutralizedwith ammonia or caustic potash or caustic soda to the methyl orange endpoint so as to eliminate the acidity due to any sulfonic acid employedas a catalyst. If desired, any residual carboxyl acidity can beeliminated by further neutralization.

Attention is directed to the following fact. The oxylkylated resinsherein used as intermediate materials for further reaction to providemore complex derivatives are characterized by having certain minimumhydrophile properties as described, and it is'particularly desirablethat these hydrophile properties be sufiicient to produce an emulsionwhen mixed with xylene in the manner previously described.

Needless to say, when a derivative is formed, such derivative may havesomewhat altered hydrophile character, or, stated another way, may

.have an altered hydrophobe-hydrophile balance.

If an ester is prepared from a high molal acid, hydrophile character isincreased. If such ester is prepared from sulfo benzoic acid or thelike, the hydrophile character may be enhanced. This is also true ineven more complicated derivatives, such as the introduction of-aquaternary nitrogen atom radical. In the formation of esters, thehydrophobe-hydrophile balance affected by the factor of whether oneprepares a complete or partial ester. In a general way, although theherein described compounds are valuable for various purposes,particularly demulsification, even though the 'hydrophobe character maybe increased'somewhat and the hydrophile character decreased, yet whenthe same test is applied to the derivatives as is applied to theoxyalkylated resins and when-such derivatives also show at least suchminimum hydrophile character, they are unquestionably most advantageous,particularly for use as demulsifiers. Thus, in the hereto appendedclaims in pointing out the invention in such specific character, atleast part of the claims are directed to the derivatives in which thederivative meets the same final test in regard to the production of axylene emulsion. Stated another way, the final derivative must be atleast as hydrophile or more so than the minimum requirement for theoxyalkylated resin as defined. -*Weclaim: x

1. An ester in which the acyl radical is that of the fatty acid of. ahydroxyacetylated blown ricinoleic acid compound selected from the classconsisting of blown castor oil, blown triricinolein. blown diricinolein,blown monoricinolein, blown superglycerinated castor oil,superglycerinated blown castor oil, blown ricinoleic acid blownpolyricinoleic. acid and blown castor oil estolides, and the alcoholicradical is that of certain hydrophile polyhydric synthetic products;said hydrophile synthetic products being oxyalkylatlon products of (A)an alpha-beta alkylene oxide having not more than 4 carbon atoms andselected from the class consisting of ethylene oxide, propylene oxide,butylene oxide, glycide and methylglycide, and (B)- anoxyalkylation-susceptible, fusible, organic solvent-soluble,water-insoluble phenol aldehyde resin; said resin being derived byreaction between a. difunctional monohydric phenol and an aldehydehaving not over 8 carbon atoms and having one functional group reactivetoward said phenol; said resin being formed in the substantial absenceof phenols of functionality greater than two; said phenol being of theformula in which R is a hydrocarbon radical having at least 4 and notmore than 12 carbon atoms and substituted in one of the positions orthoand para; said oxyalkylated resin being characterized by theintroduction into the resin molecule at the phenolic hydroxyls of aplurality of divalent radicals having the formula (R) :4, in which R1 isa member selected from the class consisting of ethylene radicals,propylene radicals, butylene radicals, hydroxypropylene radicals, andhydroxybutylene radicals, and n is a numeral varying from 1 to 20; withthe proviso that at least 2 moles of alkylene oxide be introduced foreach phenolic nucleus.

2. An ester in which the acyl radical is that of the fatty acid of ahydroxyacetylated blown ricinoleic acid compound selected from the classconsisting of blown castor oil, blown triricinolein, blown diricinolein,blown monoricinclein, blown superglycerinated castor oil,superglycerinated blown castor oil, blown ricinoleic acid, blownpolyricinoleic acid and blown castor oil estolides, and the alcoholicradical is that of certain hydrophile polyhydric synthetic products;said hydrophile synthetic products being oxyethylation products of (A)ethylene oxide, and (B) an oxyethylation-susceptible, fusible, organicsolventsoluble, water-insoluble phenol-aldehyde resin; said resin beingderived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and having one functional groupreactive toward said phenol; said resin being formed in the substantialabsence of phenols of functionality greater than two; said phenol beingof the formula in which R is a hydrocarbon radical having at least 4 andnot more than 12 carbon atoms and substituted in one of the positionsortho and para; said oxyethylated resin being characterized by theintroduction into the resin molecule at the phenolic hydroxyls of aplurality of divalent radicals having the formula (CzHaOM; wherein n isa numeral varying from 1 to 20; with the proviso that at least 2 molesof ethylene oxide be introduced for each phenolic nucleus; and with thefinal proviso that the hydrophile properties of said ester, as Well assaid oxyethylated resin, in an equal weight of xylene are sufficient toproduce 10 an emulsion when said xylene solution is shaken vigorouslywith one to three volume of water.

3. An ester in which the acyl radical is that of the fatty acid of ahydroxyacetylated blown ricinoleic acid compound selected from the classconsisting of blown castor oil, blown triricinolein, blown diricinolein,blown monoricinolein, blown superglycerinated castor oil,superglycerinated blown castor oil, blown ricinoleic acid, blownpolyricinoleic acid and blown castor oil estolides, and the alcoholicradical is that of certain hydrophile polyhydric synthetic products;said hydrophile synthetic products being oxyethylation products of (A)ethylene oxide; and (B) an oxyethy1ation-susceptib1e, fusible, organicsolventsoluble, water-insoluble, low-stage phenol-formaldehyde resinhaving an average molecular weight corresponding to at least 3 and notover 7 phenolic nuclei per resin molecule; said resin being derived byreaction between a difunctional monohydric phenol and formaldehyde; saidresin being formed in the substantial absence of phenols offunctionality greater than two; said phenol being of the formula inwhich R is an aliphatic hydrocarbon radical having at least 4 and notmore than 12 carbon atoms and substituted in one of the positions orthoand para; said oxyethylated resin being characterized by theintroduction into the resin molecule at the phenolic hydroxyls of aplurality of divalent radicals having the formula (C2H4O) n wherein n isa numeral varying from 1 to 20; with the proviso that at least 2 molesof ethylene oxide be introduced for each phenolic nucleus; and with thefinal proviso that the hydrophile properties or said ester, as well assaid oxyethylated resin, in an equal weight of xylene are sufficient toproduce an emulsion when said xylene solution is shaken vigorously withone to three volumes of water.

a. The product of claim 2 wherein R is substituted in the para position.

5. The product of claim 2 wherein R is a butyl radical substituted inthe para position.

6. The product of claim 2 wherein R is an amyl radical substituted inthe para position.

'7. The product of claim 2 wherein R is a nonyl radical substituted inthe para position.

8. The product of claim 3 wherein R is substituted in the para position.

9. The product of claim 3 wherein R is a butyl radical substituted inthe para position.

10. The product of claim 3 wherein R is an amyl radical substituted inthe para position.

11. The product of claim 3 wherein R is a nonyl radical substituted inthe para position.

MELVIN DE GROOTE. BERNHARD KEISER.

No references cited.

1. AN ESTER IN WHICH THE ACYL RADICAL IS THAT OF THE FATTY ACID OF AHYDROXYACETHYLATED BLOWN RICINOLEIC ACID COMPOUND SELECTED FROM THECLASS CONSISTING OF BLOWN CASTOR OIL, BLOWN TRICICINOLEIN, BLOWNDIRICINOLEIN, BLOWN MONORICINOLEIN, BLOWN SUPERGLYCERINATED CASTOR OIL,SUPERGLYCERINATED BLOWN CASTOR OIL, BLOWN RICINOLEIC ACID, BLOWNPOLYRICINOLEIC ACID AND BLOWN CASTOR OIL ESTOLIDES, AND THE ALCOHOLICRADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS;SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A)AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS ANDSELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDEBUTYLENE OXIDE, GLYCIDE METHYLGLYCIDE, AND (B) ANOXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE,WATER-INSOLUBLE, PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFINCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARDSAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OFPHENOLS OF FUNCTIONALITY GREATER THAN TWO; SAID PHENOL BEING OF THEFORMULA